铜铁络合物的合成及光解水性能研究

发布时间：2018-04-26 23:28

  本文选题：Kn(?)lker铁 + 铜光敏剂　； 参考：《浙江工业大学》2016年硕士论文

【摘要】：利用太阳能直接分解水使其光能转换成氢气化学能,是当今新能源的研究前沿,也是全球关注的十大科学难题之一。高效、稳定、价廉、无毒的光能转换催化产氢体系是光解水系统中的核心部分,也是目前制约太阳能利用效率的关键问题。本文拟以铜-铁组建的非贵金属光解水制氢体系为研究对象,设计合成新型氮磷杂配铜基光敏剂和铁基催化剂,探索其光催化性能及其作用机理。首先以邻氨基苯甲醛或邻氨基苯甲酰类衍生物和环己二酮为原料,进行Friedlander缩合反应合成菲咯啉衍生物—6,7-二氢苯并菲咯啉(A-C),然后以5,8-二苯基-6,7-二氢苯并菲咯啉(C)为原料,Pd/C催化脱氢芳构化得到5,8-二苯基-6,7-苯并菲咯啉(D)。以这些菲咯啉衍生物A-D为氮配体,以XantPhos(Ⅰ)和2,8-二甲基-4,6-双(2,8-二甲基氧膦杂蒽-10基)氧硫杂蒽(Ⅱ)为膦配体,通过原位配位形成铜(Ⅰ)氮磷杂配络合物,研究其在均相光解水制氢体系中的光敏性能。结果表明,以2,8-二甲基-4,6-双(2,8-二甲基氧膦杂蒽-10基)氧硫杂蒽(Ⅱ)为膦配体,5,8-二苯基-6,7-二氢苯并菲咯啉(C)为氮配体合成的铜光敏剂具有最高光敏活性,制氢催化转换数TON达441,稳定性可达15h。通过光物理性质和电化学表征证实长寿命的铜光敏剂激发态有利于提高光敏制氢活性。理论计算研究结果指出这类铜配合物主要跃迁模式是配体到配体的跃迁,而且进一步证实了氮配体的6,7位C-C单键结构可以增大能力间隙和增加氮配体在HOMO轨道的电子云密度,从而提高了光敏活性。Kn(?)lker’s铁已在各类还原反应中被证实是高效催化剂,然而尚未见其在光解水中的催化性能研究。以Cu(Xantphos)(4,7-二苯基-2,9-二甲基-1,10-菲咯啉)(CuPS G I)作为光敏剂,发现碱活化原位形成的Kn(?)lker’s铁具有良好的光解水制氢催化性能,制氢的速度为常用的Fe_3(CO)_(12)催化剂的15倍。通过荧光淬灭、循环伏安和质谱跟踪等实验证实还原淬灭机理和Kn(?)lker’s铁催化过程。总之,通过配体调控研究了铜铁组建的均相光解水催化体系,获得了其构效关系及作用机理,为深入理解和开发高效光解水体系提供一些理论研究支撑。
[Abstract]:Using solar energy to decompose water directly to convert its light energy into hydrogen chemical energy is the frontier of new energy research and one of the ten scientific problems that the world pays close attention to. Efficient, stable, inexpensive and non-toxic photo-energy conversion catalytic hydrogen production system is the core part of the photodissociation water system, and also the key problem that restricts the efficiency of solar energy utilization. In this paper, a new type of nitro-phosphorous heteropoly copper-based Guang Min and iron-based catalysts were designed and synthesized, and their photocatalytic properties and mechanism were explored. First of all, using o-aminobenzaldehyde or o-aminobenzoyl derivatives and cyclohexanedione as raw materials, Phenanthroline derivative -6- (7-dihydrobenzophenanthroline) was synthesized by Friedlander condensation reaction and then dehydroaromatization was carried out by catalytic dehydroaromatization of 5 ~ (8) -diphenyl-6-dihydrobenzophenanthroline (C) as a starting material for the synthesis of 5 ~ (8) -diphenyl-6- (benzophenanthroline) -diphenanthroline (DX) as a catalyst for the dehydroaromatization of 5 ~ (8) -diphenyl-6- (phenanthroline). These phenanthroline derivatives A-D were used as nitrogen ligands and XantPhos1 (鈪，

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